Oxime derivatives for protecting plant crops

ABSTRACT

Certain oximes of the general formula ##STR1## are employed as antidotes to protect crop plants from the adverse action of haloacetanilide and 1,3,5-trazine herbicides.

This is a division of application Ser. No. 068,263 filed on Aug. 20,1979, now U.S. Pat. No. 4,353,735.

The present invention relates to a method of protecting plant crops fromthe phytotoxic action of potent herbicides by means of oxime derivativesand also to a number of novel oxime derivatives.

The oxime derivatives employed as active compounds have the formula I##STR2## wherein n is 0, 1 or 2 and m is 0 or 1, and

Ar is a phenyl radical ##STR3## a naphthyl radical substituted by R₂ andR₃, a 5- to 10-membered heterocyclic radical which contains not morethan 3 identical or different heteroatoms N, O and/or S and which issubstituted by R₂, R₃ and R₄ and can be substituted by oxo or thiono, orif m is 0, Ar is a radical R--CO, wherein R is a radical --OR₅, in whichR₅ is an aliphatic group containing not more than 8 carbon atoms or isan araliphatic group containing not more than 15 carbon atoms or is acycloaliphatic or aromatic group, each containing not more than 10carbon atoms, while the possible substituents of the aromatic radicalsor of the cycloaliphatic radical are halogen, --CN, --NO₂, lower alkyl,lower alkoxy, haloalkyl; or R is a radical --NH--CO--NH--R₇ or a radical--N(R₆)(R₇), wherein R₆ is hydrogen or lower alkyl and R₇ is hydrogen oran aliphatic group containing not more than 8 carbon atoms or anaraliphatic group containing not more than 15 carbon atoms, or acycloaliphatic or aromatic group containing not more than 10 carbonatoms, while possible substituents of the aromatic groups or of thecycloaliphatic radical are halogen, --CN, NO₂, lower alkyl, loweralkoxy, or haloalkyl; or R is a radical --N(R₆)(R₇), wherein R₆ and R₇together form a 5- or 6-membered heterocyclic ring which canadditionally contain oxygen as possible further heteroatom,

R₁ is hydrogen, halogen, lower alkyl, lower alkoxy or a p-phenoxyradical which is unsubstituted or at most disubstituted by halogen, CN,NO₂, CF₃,

R₂, R₃ and R₄, each independently of the other, are hydrogen, halogen,CN, NO₂, lower alkyl, lower alkoxy, haloalkyl, haloalkoxy, loweralkanoyl, OH, phenyl, halophenyl, lower carbalkoxy, loweralkoxycarbonyl, lower alkoxycarbonyloxy, lower carbamoyloxy, loweralkylthio, lower alkylsulfonyl, phenalkoxy, cyclohexyl, NH₂, --NH-loweralkyl, --N(di-lower alkyl), lower alkanoylamino, carbamoyl, sulfamoyl,

X is hydrogen, --CN, halogen, lower alkyl, lower alkanoyl, --COOH, acarboxylic acid ester radical, a carbamoyl radical, and

Q is the radical --C_(a) H_(2a) --R₈, wherein a is an integer between 1and 6, while the corresponding radical can also be branched and R₈ isone of the following radicals: ##STR4## wherein R₉ is hydrogen, acycloaliphatic, araliphatic or aromatic group which is unsubstituted ormono- or polysubstituted at the ring by CN, NO₂, halogen, lower alkyl,lower alkoxy or haloalkyl, or is lower alkenyl, lower haloalkenyl orlower alkynyl, R₁₀ is an aliphatic group or a cycloaliphatic,araliphatic or aromatic group which is unsubstituted or mono- orpolysubstituted at the ring by CN, NO₂, halogen, lower alkyl, loweralkoxy or haloalkyl, R₁₁ is hydrogen, lower alkyl or cycloalkyl, R₁₂ islower alkyl or an aromatic group, while Y is O, S, SO, SO₂ or ##STR5##and A is C₂ -C₃ alkylene or C₂ -C₃ alkenylene which is unsubstituted orsubstituted by halogen, CN or lower alkyl and which together with acarbon chain which is unsubstituted or substituted by halogen, CN orlower alkyl can form a fused ring, and Hal is halogen.

By halogen in formula I is meant fluorine, chlorine, bromine or iodine.

Carboxylic acid esters are lower alkyl esters. Carbamoyl radicals, inaddition to --CONH₂, are also monoalkyl-substituted or symmetrically orunsymmetrically dialkyl-substituted amides, while the alkyl groups arelower alkyl groups.

The term alkyl by itself or as moiety of another substituent comprisesbranched or unbranched alkyl groups of 1 to 8 carbon atoms. Lower alkylby itself or as moiety of another substituent denotes C₁ -C₄ alkyl.Examples are methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec-butyl, tert-butyl, as well as the higher homologues amyl, isoamyl,hexyl, heptyl, octyl, together with their isomers. By analogy, alkanoylor cyanoalkyl groups contain an additional carbon atom. Lower alkenyl oralkynyl groups accordingly contain not more than 4 carbon atoms.

The term "aliphatic group" comprises saturated radicals (alkyls), andunsaturated radicals (alkenyls, alkadienyls, alkynyls),halogen-substituted radicals, cyano-substituted radicals, and radicalswhich are interrupted by oxygen. These radicals contain not more than 8carbon atoms.

The term "aromatic group" comprises phenyl and naphthyl, which can inprinciple be mono- or polysubstituted by CN, NO₂, halogen, lower alkyl,lower alkoxy or haloalkyl. An araliphatic radical comprises anunsubstituted or mono- to trisubstituted phenyl or naphthyl radicalwhich is bonded through lower alkyl or lower alkenyl to the radical ofthe molecule. Examples are benzyl, phenethyl, phenylallyl and theirhomologues.

Unsubstituted or substituted heterocyclic radicals can be mono- orbicyclic. Examples are:

furan, nitrofuran, bromofuran, methylfuran, thiophene, chlorothiophene,pyridine, 2,6-dichloropyridine, pyrimidine, pyridazine, pyrazine,piperidine, methylpiperidine, morpholine, thiomorpholine,tetrahydrofurane, oxazole, pyrazole, pyrrole, pyrroline, pyrrolidine,thiazole, 2,3-dihydro-4H-pyrane, pyrane, dioxane or 1,4-oxathi-(2)-ine,benzthiazole, benzoxazole, benzimidazole, quinoline, benz-1,3-dioxolane.Cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyland cycloheptyl. Cycloaliphatic radicals correspond to these ringsystems, but, where possible, can additionally contain one or moredouble bonds.

The compounds of the formula I can be obtained

(a) with the exception of compounds, wherein Q is --C.tbd.C Hal, byreacting a compound of the formula II ##STR6## with a compound of theformula III

    Hal'--Q                                                    (III)

or

(b) where Q is --C.tbd.C Hal, by reacting a compound of the formula IV##STR7## with halogen in the presence of a base. In the above formulaeII, III and IV, Ar, X, Q, m and n are as defined for formula I, Hal' ishalogen, preferably chlorine or bromine, and Me is hydrogen or a metalcation, preferably an alkali metal or alkaline earth metal cation.

The compounds of the formula IV can be obtained by a process analogousto that of process (a).

The reactions can be carried out in the presence or absence of solventswhich are inert to the reactants. Examples of suitable solvents are:alcohols, such as ethanol; ketones, such as acetone; nitriles, such asacetonitrile; N,N-dialkylated amides, such as dimethyl formamide;dimethyl sulfoxide, pyridine, or, in process (b), also water as well asmixtures of these solvents with one another.

Where Me is hydrogen, the process is carried out in the presence of abase, Examples of suitable bases are inorganic bases, such as theoxides, hydroxides, hydrides, carbonates and bicarbonates of alkalimetals and alkaline earth metals, as well as e.g. tertiary amines, suchas trialkylamines (e.g. triethylamine), and pyridine. The reactiontemperatures are in the range between 0° and 150° C. The reactions arecarried out under normal pressure and, in (a), optionally in a nitrogenatmosphere.

The compounds of the formula II are prepared by methods analogous toknown ones. Processes (a) and (b) also constitute an object of theinvention.

The compounds of the formula I can be used by themselves or togetherwith suitable carriers and/or other adjuvants. Suitable carriers andadjuvants can be solid or liquid and correspond to the substancesnormally used in the art of formulation, for example natural orregenerated mineral substances, solvents, dispersants, wetting agents,tackifiers, thickeners, binders or fertilisers.

The content of active substance in commercial compositions is between0.1% and 90% by weight.

For application, the compounds of the formula I may be processed to thefollowing formulations (in which the percentages by weight in bracketsrefer to advantageous amounts of active ingredient):

Solid formulations:

dusts, tracking agents, (up to 10%) granules (coated granules,impregnated granules and homogeneous granules); pellets (1 to 80%);

Liquid formulations:

(a) active substance concentrates which are dispersible in water:wettable powders, pastes; (25-90% in commercial packs, 0.01 to 15% inready for use solutions; emulsifiable concentrates and concentratedsolutions (10 to 50%; 0.01 to 15% in ready for use solutions).

(b) Solutions (0.1 to 20%); aerosols.

Such compositions also constitute an object of the invention.

Different compounds which are able to antagonise the harmful action of aherbicide on cultivated plants specifically have already been proposedas antidotes, i.e. compounds which protect cultivated plants withoutnoticeably influencing the herbicidal action on the weeds which it isdesired to control. Depending on their properties, such antidotes, alsoknown as safeners, can be used for pretreating the seeds of thecultivated plants (dressing seeds or seedlings) or before sowing seedsin furrows or as tank mixture, by themselves or together with theherbicide or after emergence of the plants. The pre-emergence treatmentincludes both treatment of the crop area before sowing (ppi=pre-plantincorporation) and treatment of the crop areas after sowing but beforeemergence of the plants.

Thus, British patent specification No. 1 277 557 discloses the treatmentof seed and seedlings of wheat and sorghum with certain esters andamides of oxamic acid before attack byN-methoxymethyl-2'-6'-diethyl-chloroacetanilide (Alachlor). Otherpublications (German Offenlegungsschriften 1 952 910 and 2 245 471, andFrench patent specification 2 021 611), propose antidotes for thetreatment of cereals, maize seeds and rice seeds to protect them againstattack by herbicidal thiolcarbamates. In German patent specification 1576 676 and U.S. patent specification 3 131 509,hydroxyamino-acetanilides and hydantoins are suggested for protectingcereal seeds against carbamates, such as IPC, CIPC, etc.

The further development, however, has shown all these preparations to beunsatisfactory.

Surprisingly, oximes of the formula I have the property of protectingcultivated plants from attack by aggressive agricultural chemicals, inparticular herbicides, of the most diverse compound classes, including1,3,5-triazines, 1,2,4-triazinones, phenylurea derivatives, carbamates,thiolcarbamates, phenoxyacetates, phenoxypropionates, haloacetanilides,halophenoxyacetates, substituted phenoxyphenoxyphenoxyacetates and-propionates, benzoic acid derivatives, where these compounds are nottolerated or insufficiently tolerated by plants.

The rates of application of the antidote with respect to the herbicidedepend largely the mode of application. Where a field treatment iscarried out, the ratio of antidote of the formula I to phytotoxicchemical is 1:100 to 5:1, preferably 1:20 to 1:1. When dressing seedsand taking similar specific protective measures, however, much loweramounts of antidote are required in comparison with e.g. the amounts ofherbicide later employed per hectare of crop area (e.g., about 1:3000 to1:1000). As a rule, protective measures such as seed dressing with anantidote of the formula I and possible later field treatment withagricultural chemicals are only loosely connected. Pretreated seeds andplants can later come into contact with different chemicals inagriculture, horticulture and forestry.

Accordingly, the invention relates to plant protection compositionswhich contain, as active ingredient, solely an antidote of the formula Itogether with conventional carriers. If appropriate or desired, suchcompositions can additionally be mixed with the chemical against theaction of which it is desired to protect the cultivated plant, forexample with a herbicide.

Cultivated plants within the scope of this invention are all plantswhich, in any form, can be harvested (seeds, roots, stalks, tubers,leaves, blossoms) and from which extracts can be obtained (oils, sugar,starch, protein) and which for this purpose are cultivated and tended.To these plants being e.g. all species of cereals, maize, rice, millet,soybeans, beans, peas, potatoes, vegetables, cotton, sugar beet, sugarcane, ground nuts, tobacco, hops, and also ornamentals, fruit trees andbananas, cocoa and natural rubber plants.

In principle, an antidote can be employed wherever it is desired toprotect a cultivated plant from the phytotoxicity of a chemical.

The invention also relates to a method of protecting cultivated plantsfrom aggressive (phytotoxic) chemicals, which comprises applying anoxime derivative of the formula I which acts as antidote, optionallybefore or after application of the chemical, or also simultaneously withthe chemical.

The invention also relates to the propagation products of suchcultivated plants which are given a protective treatment with an oximederivative of the formula I. By propagation products are meant allgenerative parts of plants which can be used for the propagation of thecultivated plant, for example grains (seeds in the narrow sense), roots,fruit, tubers, rhizomes, parts of stalks, branches (seedlings) and otherparts of plants. Propagation products also include pregerminated plantsand young plants which, after pregermination or emergence, will befurther transplanted. Such young plants can be selectively protected bymeans of a complete or partial immersion treatment beforetransplantation.

The following types of substituent or combinations thereof with oneanother are preferred: ##STR8## (d) benzoxazole (e) benzthiazole

for X:-

(a) cyano

(b) hydrogen

(c) a carboxylic acid ester radical

(d) lower alkyl

for n and m:-

(a) n=2 m=1

(b) m=0

The invention is illustrated by the following Examples, but without anyrestriction to what is described therein. Temperatures are in degreescentigrade, pressures in millibars, and parts and percentages are byweight.

PREPARATIVE EXAMPLES EXAMPLE 1

Manufacture of ##STR9## 8.4 g (0.05 mole) of the sodium salt ofα-phenylacetonitrile oxime were dissolved in 50 ml of dimethylformamide. With stirring, 7.8 g of chloromethylbenzyl ether were addedto this solution at room temperature. After it had been stirred for 8hours, the reaction mixture was washed with water and extracted withethyl acetate. The ethyl acetate solution was dried over sodium sulfateand concentrated in vacuo, affording the oily product of the aboveformula; n_(D) ²² 1.5621.

EXAMPLE 2 ##STR10##

A mixture of 6 g of the sodium salt of α-phenylacetonitrile oxime and5.5 g of N-chloromethylsuccinimide in 30 ml of dimethyl formamide wasstirred under nitrogen for 17 hours at 50° C. The reaction mixture wasdiluted with ethyl acetate, washed with water, dried and concentrated,affording 9.4 g of a crystalline product with a melting point of135°-138° C. (Recrystallisation from chloroform/petroleum ether).

EXAMPLE 3

Manufacture of ##STR11##

23 g of α-phenylacetonitrile propargyloxime was dissolved in 150 ml ofmethanol. With stirring and cooling with ice water, 29.5 g of iodine in100 ml of sodium hydroxide were added in portions at 5° to 10° C. in thecourse of 30 minutes. When the addition was complete, the reactionmixture was stirred for 4 hours at 5° to 10° C. The suspension was thenfiltered by suction and the filter cake was washed with water and driedin vacuo at 40°-50° C., affording 33.5 g of the final product with amelting point of 84°-85° C.

The following compounds of the formula (I) can be obtained in analogousmanner or by one of the methods described herein.

    __________________________________________________________________________     ##STR12##                                                                    Compound                                                                            R.sub.1                                                                            R.sub.2  R.sub.3 m X     Q                Physical data                                                                 (°C.)             __________________________________________________________________________    1     H    H        H       0 CN    CH.sub.2 CCl     m.p. 83-85°       2     H    4-Br     H       0 CN    CH.sub.2 CCl     oil                      3     3-Cl 4-Cl     H       0 CN    CH.sub.2 CCl     m.p. 77-79°       4     2-Cl 4-Cl     H       0 CN    CH.sub.2 CCl     m.p. 92-95°       5     H    4-CH.sub.3 O                                                                           H       0 CN    CH.sub.2 CCl     m.p.                                                                          132-134°          6     H    4-CH.sub.3                                                                             H       0 CN    CH.sub.2 CCl     m.p. 98-100°      7     3-CH.sub.3                                                                         4 CH.sub.3                                                                             H       0 CN    CH.sub.2 CCl     m.p. 77-79°       8     H    4-Cl     H       0 CN    CH.sub.2 CCl     m.p. 84-85°         9   H    H        H       0 CN                                                                                   ##STR13##       m.p.                                                                          174-178°            10  H    H        H       0 CN                                                                                   ##STR14##                                  11  H    H        H       0 COOCH.sub.3                                                                          ##STR15##                                  12  H    H        H       0 COOCH.sub.3                                                                          ##STR16##                                  13  H    H        H       0 CH.sub.3                                                                             ##STR17##                                  14  H    H        H       0 CN                                                                                   ##STR18##                                  15  H    4-Cl     H       0 CN                                                                                   ##STR19##                                  16  3-Cl 4-Cl     H       0 CN                                                                                   ##STR20##                                  17  H    4-(t)-C.sub.4 H.sub.9                                                                  H       0 CN                                                                                   ##STR21##                                  18  H    4-CH.sub.3 O                                                                           H       0 CN                                                                                   ##STR22##                                  19  3-CH.sub.3                                                                         4-CH.sub.3                                                                             H       0 CN                                                                                   ##STR23##                                  20  H    4-Cl     H       0 CN                                                                                   ##STR24##                                   21 2-Cl 4-Cl     H       0 CN    CH.sub.2OCH.sub.2C.sub.6 H.sub.5                                                               n.sub.D.sup.22                                                                1.5745                   22    H    H        H       0 CN    CH.sub.2OCH.sub.2C.sub.6 H.sub.5                                                               n.sub.D.sup.22                                                                1.5621                   23    2-Cl 4-Cl     H       0 CN    CH.sub.2CH.sub.2OCHCH.sub.2                                                                    n.sub.D.sup.38                                                                1.5510                   24    H    H        H       0 CN    CH.sub.2CH.sub.2OCHCH.sub.2                                                                    n.sub.D.sup. 25                                                               1.5362                   25    H    4-OC.sub.6 H.sub.4 F.sub.3 (4')                                                        H       0 CN    CH.sub.2OCH.sub.2C.sub.6 H.sub.5          26    H    H        H       1 CN    CH.sub.2CCl                               27    H    4-CH.sub.3                                                                             H       1 CN    CH.sub.2CCl                               28    H    4-Cl     H       1 CN    CH.sub.2CCl                               29    3-Cl 4-Cl     H       1 CN    CH.sub.2, CCl                             30    H    4-CH.sub.3 O                                                                           H       1 CN    CH.sub.2CCl                               31    H    2-Cl     H       1 CN    CH.sub.2CCl                               32    2-Cl 4-Cl     H       1 CN    CH.sub.2 CCl                              33    3-Cl 4-Cl     H       1 COOCH.sub.3                                                                         CH.sub.2CCl                               34    4-Cl H        H       1 COOCH.sub.3                                                                         CH.sub.2C Cl                              35    H    H        H       1 COOCH.sub.3                                                                         CH.sub.2CCl                               36    H    H        H       1 COOC.sub.2 H.sub.5                                                                  CH.sub.2CCl                               37    H    H        H       0 CN    CH.sub.2CH.sub.2OH                                                                             m.p. 56°          38    2-Cl 4-Cl     H       0 CN    CH.sub.2CH.sub.2OH                                                                             n.sub.D.sup.26                                                                1.6181                   39    H    4-Cl     H       0 CN    CH.sub.2CH.sub.2OH                                                                             m.p. 50°          40    H    H        H       0 CN    CH.sub.2 CH.sub.2 OCONHC.sub.6                                                H.sub.3 Cl.sub.2 (3,4)                                                                         m.p. 77-78°       41    H    H        H       0 CN    CH.sub.2 CH.sub.2 OCONHC.sub.6                                                H.sub.4 CF.sub.3 (3)                                                                           n.sub.D.sup.20 =                                                              1.5434                   42    H    H        H       0 CN    CH.sub.2 CH.sub.2 OCONHC.sub.6                                                H.sub.4 Cl(4)    m.p. 94-95°       43    H    H        H       0 CN    CH.sub.2 CH.sub.2 OCONHC.sub.6                                                H.sub.5          m.p. 71-72°       44    H    H        H       0 CN    CH.sub.2 CH.sub.2 OCONHCH.sub.3                                                                m.p. 57-58°       45    H    H        H       0 CN    CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.                                                            n.sub.D.sup.26 =                                                              1.5297                   46    H    H        H       0 CN    CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  n.sub.D.sup.26                                                                1.5322                   47    H    H        H       0 CN    CH.sub.2 CH.sub.2 OCOCH.sub.2                                                                  n.sub.D.sup.25                                                                1.5455                   48    H    H        H       0 H     CH.sub.2 CH.sub.2 OCOC.sub.6 H.sub.5                                                           n.sub.D.sup.23 =                                                              1.5745                   49    2-Cl 4-Cl     H       0 H     CH.sub.2CCl      m.p. 92-94°       50    2-Cl 6-Cl     H       0 H     CH.sub.2CCl      m.p. 83-84°       51    3-Cl 4-Cl     H       0 H     CH.sub.2CCl      m.p. 83-84°       52    H    3-NO.sub.2                                                                             H       0 H     CH.sub.2CCl      m.p.                                                                          113-114°          53    H    4-NO.sub.2                                                                             H       0 H     CH.sub.2CCl      m.p.                                                                          198-199°          54    H    4-CN     H       0 COOCH.sub.3                                                                         CH.sub.2CH.sub.2OC.sub.6 H.sub.5          55    H    4-CN     H       0 CH.sub.3                                                                            CH.sub.2CH.sub.2OCONHCH.sub.3             56    H    4-CN     H       0 CN    CH.sub.2CH.sub.2OCONHCH.sub.3             57    H    4-CN     H       0 CN    CH.sub.2CH.sub.2OCOCH.sub.3               58    H    2-CN     H       0 CN    CH.sub.2CH.sub.2OCOCH.sub.3               59    H    4-NO.sub.2                                                                             H       0 CH.sub.3                                                                            CH.sub.2CCl                               60    H    4-NO.sub.2                                                                             H       0 CN    CH.sub.2CCl                               61    H    2-CH.sub.3                                                                             4-OCONHCH.sub.3                                                                       0 CH.sub.3                                                                            CH.sub.2CH.sub.2OCONHCH.sub.3               62  3-OCH.sub.3                                                                        2-NO.sub.2                                                                             4-OCOCH.sub.3                                                                         0 CN                                                                                   ##STR25##                                  63  3-Cl 2-OCOCH.sub.3                                                                          5-Cl    0 CH.sub.3                                                                            CH.sub.2OC.sub.6 H.sub.5                  64    4-CH.sub.3                                                                         2-OCOCH.sub.3                                                                          6-CH.sub.3                                                                            0 H     CH.sub.2 CH.sub.2NHCOC.sub.6 H.sub.5      65    H    4-N(C.sub.2 H.sub.5).sub.2                                                             H       0 CH.sub.3                                                                            CH.sub.2 CH.sub.2NHCOCH.sub.3             66    3-CH.sub.3                                                                         5-CH.sub.3                                                                             H       0 CH.sub.3                                                                            CH.sub.2 CH.sub.2OCH.sub. 2 C.sub.6                                           H.sub.3 Cl.sub.2 (2,4)                    67    H    4-Cyclo- H       0 H     CH.sub.2 CH.sub.2OH                                  hexyl                                                              68    H    4-Br     H       0 CONHCH.sub.3                                                                        CH.sub.2 CH.sub.2SCH.sub.2C.sub.6                                             H.sub.5                                     69  H    2-OCH.sub.2 C.sub.6 H.sub.5                                                            H       0 CH.sub.3                                                                             ##STR26##                                  70  H    4-C.sub.6 H.sub.4 Br(4)                                                                H       0 CH.sub.3                                                                             ##STR27##                                  71  H    4-OCH.sub.2 C.sub.6 H.sub.5                                                            H       0 CH.sub.3                                                                            CH(CH.sub.3)NHCOCH.sub.3                  72    H    4-CHCHC.sub.6 H.sub.5                                                                  H       0 CH.sub.3                                                                            CH(CH.sub.3)CH.sub.2NCHO                    73  3-Cl 2-OCOCH.sub.3                                                                          6-Cl    0 C.sub.2 H.sub.5                                                                      ##STR28##                                  74  3-Cl 2-OCOCH.sub.3                                                                          6-Cl    0 CH.sub.3                                                                            CH.sub.2 CH.sub. 2OCOCH.sub.2 Cl          75    5-Cl 2-OCONHCH.sub.3                                                                        H       0 CH.sub.3                                                                            CH.sub.2CH.sub.2 N(CH.sub.3)COfuryl-                                          (2)                                       76    H    4-CH.sub.3 O                                                                           H       0 CN    CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5                                                             n.sub.D.sup.24                                                                1.5785                   77    H    4-CH.sub.3                                                                             H       0 CN    CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5                                                             n.sub.D.sup.24                                                                1.5655                   78    H    4-CH.sub.3                                                                             H       0 CN    C.sub.2 H.sub.4 OCHCH.sub.2                                                                    n.sub.D.sup.24                                                                1.5159                   79    H    4-Cl     H       0 CN    C.sub.2 H.sub.4 OCHCH.sub.2                                                                    m.p. 41-43°       80    H    H        H       0 CN    CH(CH.sub.3)CH.sub.2 OH                                                                        n.sub.D.sup.25                                                                1.5492                   81    H    H        H       0 CN    CH.sub.2 SCH.sub.2 C.sub.6 H.sub.5                                                             n.sub.D.sup.25                                                                1.5952                   82    H    4-Cl     H       0 CN    CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5                                                             n.sub.D.sup.23                                                                1.5604                   83    H    4-Cl     H       0 CN    C.sub.2 H.sub.4 OCH.sub.2 C.sub.6                                             H.sub.5          m.p. 74-75°       84    H    H        H       0 CN    C.sub.2 H.sub.4OC.sub.6 H.sub.5                                                                m.p. 70-71°       85    H    4-CH.sub. 3                                                                            H       0 CN    C.sub.2 H.sub.4OC.sub.6 H.sub.5                                                                m.p. 84-85°       86    H    4-OCH.sub.3                                                                            H       0 CN    C.sub.2 H.sub.4OC.sub.6 H.sub.5                                                                m.p. 76-77°       87    H    4-OCH.sub.3                                                                            H       0 CN    C.sub.2 H.sub.4OCHCH.sub.2                                                                     m.p. 57-58°       88    H    4-OCH.sub.3                                                                            H       0 CN    CH(CH.sub.3)CH.sub.2OH                                                                         n.sub.D.sup.24 =                                                              1.5379                     89  H    H        H       1 CN                                                                                   ##STR29##       n.sub.D.sup.26 :                                                              1.5498                     90  H    H        H       1 CN                                                                                   ##STR30##       n.sub.D.sup.26 :                                                              1.5452                     91  H    H        H       1 CN                                                                                   ##STR31##       n.sub.D.sup.26 :                                                              1.5176                     92  H    H        H       1 CN                                                                                   ##STR32##       m.p. 95-7°                                                             C.                         93  H    4-Cl     H       1 CN                                                                                   ##STR33##                                  94  H    H        H       1 CN                                                                                   ##STR34##       m.p. 120-2°                                                            C.                         95  H    H        H       1 CN                                                                                   ##STR35##       m.p. 98-100°                                                           C.                         96  H    4-CH.sub.3                                                                             H       1 CN                                                                                   ##STR36##                                  97  H    H        H       1 CN                                                                                   ##STR37##       m.p. 135-7°                                                            C.                         98  H    H        H       1 CN                                                                                   ##STR38##       n.sub.D.sup.26 :                                                              1.5486                     99  H    H        H       1 CN                                                                                   ##STR39##       n.sub.D.sup.25 :                                                              1.5515                     100 H    4-Cl     H       1 CN                                                                                   ##STR40##       n.sub.D.sup.26 =                                                              1.5376                     101 H    H        4-Cl    0 CN                                                                                   ##STR41##       m.p. 152-3°         102 H    H        H       0 CN                                                                                   ##STR42##       m.p. 146-8°         103 H    H        H       0 CN                                                                                   ##STR43##       m.p. 105-6°         104 H    4-Cl     H       0 CN                                                                                   ##STR44##       m.p. 98-99°         105 2-Cl 4-Cl     H       0 H     CH.sub.2C Cl     m.p. 92-94°       106   2-Cl H        6-Cl    0 H     CH.sub.2CCl      m.p. 83-84°       107   H    3-NO.sub.2                                                                             H       0 H     CH.sub.2CCl      m.p.                                                                          113-114°          108   3-Cl 4-Cl     H       0 H     CH.sub.2CCl      m.p. 83-4°          109 H    4-CH.sub.3                                                                             H       0 CN                                                                                   ##STR45##                                  110 H    4-OCH.sub.3                                                                            H       0 CN                                                                                   ##STR46##                                  111 2-Cl 4-Cl     H       0 CN    CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5        112   3-Cl 4-Cl     H       0 CN    CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5          113 H    4-CH.sub.3                                                                             H       0 CN                                                                                   ##STR47##                                  114 H    4-CH.sub.3                                                                             H       0 CN                                                                                   ##STR48##                                  115 2-OCH.sub.3                                                                        H        H       0 CN    CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5        116   H    3-CH.sub.3                                                                             H       0 CN    CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5        117   H    3-Cl     H       0 CN    CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5        118   H    3-CN     H       0 CN    CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5        119   H    3-CF.sub.3                                                                             H       0 CN    CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5        120   H    4-Br     H       0 CN    CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5        121   H    4-F      H       0 CN    CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5          122 H    3-OCH.sub.3                                                                            H       0 CN                                                                                   ##STR49##                                  123 3-Cl 4-CH.sub.3                                                                             H       0 CN    CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5        124   H    H        H       1 CN    CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5        125   H    4-CH.sub.3                                                                             H       1 CN    CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5        126   H    4-Cl     H       1 CN    CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5        127   H    4-CH.sub.3                                                                             H       0 CH.sub.3                                                                            CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5        128   H    4-OCH.sub.3                                                                            H       0 CH.sub.3                                                                            CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5        129   H    4-Cl     H       0 CH.sub.3                                                                            CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5        130   H    4-CH.sub.3                                                                             H       0 H     CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5        131   H    4-OCH.sub.3                                                                            H       0 H     CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5        132   3-Cl 4-Cl     H       0 H     CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5        __________________________________________________________________________

                  TABLE II                                                        ______________________________________                                        (Ar = 1-napth 1; m = 0)                                                                                         Physical                                    Compound                                                                              X      Q                  data (°C.)                           ______________________________________                                        133     CN     CH.sub.2 CH.sub.2 OH                                                                             n.sub.D.sup.26 1.6172                         134   CN                                                                                    ##STR50##         m.p. 166-8°                            135   CN                                                                                    ##STR51##                                                       136   CN     CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5                                                               n.sub.D.sup.22 1.6300                       137     CN     CH.sub.2 CH.sub.2 OCHCH.sub.2                                                                    n.sub.D.sup.32 1.5918                         138   CN                                                                                    ##STR52##         m.p. 145-146°                        ______________________________________                                    

                  TABLE III                                                       ______________________________________                                         ##STR53##                                                                      Compound  Z     Q                                                           ______________________________________                                        139     S     CH.sub.2CH.sub.2NHCONHCH.sub.3                                  140     S     CH.sub.2CH.sub.2NHCONHC.sub.6 H.sub.4 Cl(4)                     141     S     CH.sub.2CH.sub.2OCONHC.sub.6 H.sub.3 Cl.sub.2 (3,4)             142     S     CH(CH.sub.3)CH.sub.2OC.sub.6 H.sub.3NO.sub.2 (2)CF.sub.3                      (4)                                                             143     O     CH.sub.2CCl                                                       144   O                                                                                    ##STR54##                                                        145   O     CH.sub.2CH.sub.2N(CH.sub.3)COC.sub.2 H.sub.5                    146     O     CH.sub.2CH.sub.2OC.sub.6 H.sub.3NO.sub.2 (2)CH.sub.3            ______________________________________                                                      (4)                                                         

                                      TABLE IV                                    __________________________________________________________________________     ##STR55##                                                                     Compound                                                                             R.sub.20                                                                         R.sub.21                                                                           ##STR56##                                                     __________________________________________________________________________    147    2-Cl                                                                             6-Cl 4-CHNOCH.sub.2CH.sub.2 N(CH.sub.3).sub.2                         148  H  H                                                                                   ##STR57##                                                       149  H  H    2-CHNOCH.sub.2OC.sub.6 H.sub.5                                 150    H  H    3-C(CH.sub.3)NOCH.sub.2CH.sub.2OC.sub.6 H.sub.5 Cl.sub.2                      (2,4)                                                            151  H  H                                                                                   ##STR58##                                                       152  H  H    3-C(CH.sub.3)NOCH.sub.2O C.sub.6 H.sub.5                       153    H  H    3-C(COOCH.sub.3)NOCH.sub.2OC.sub.6 H.sub.5                     154    H  H    CH.sub.2CCHm.p. 26°                                     __________________________________________________________________________

                                      TABLE V                                     __________________________________________________________________________     ##STR59##                                                                    Compound                                                                            Z.sub.1                                                                            R.sub.22                                                                         R.sub.23                                                                         X  Q                                                         __________________________________________________________________________    155   O    H  H  CN                                                                                ##STR60##                                                  156 O    H  H  CN                                                                                ##STR61##                                                  157 O    H  H  H  CH.sub.2CH.sub.2OCONHCH.sub.3                               158 O    H  CH.sub.3                                                                         CN                                                                                ##STR62##                                                  159 O    Cl H  CN CH.sub.2CH.sub.2CH.sub.2OCON(CH.sub.3).sub.2              160   S    H  H  CN CH.sub.2CH.sub.2OCH.sub.2C.sub.6 H.sub.5                    161 S    H  H  Cl                                                                                ##STR63##                                                  162 S    H  H  CN CH.sub.2CH.sub.2OCONHCH.sub.3                             163   S    H  CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.2CH.sub.2OCOCH.sub.3                               164   S    H  NO.sub.2                                                                         CH.sub.3                                                                         CH.sub.2CH.sub.2OH                                        165   NCH.sub.3                                                                          H  H  CN CHCCH                                                       166 NCH.sub.3                                                                          H  H  CN                                                                                ##STR64##                                                  167 NCH.sub.3                                                                          H  H  CN CH.sub.2OC.sub.6 H.sub.5                                    168 NCH.sub.3                                                                          CH.sub.3                                                                         H  CN                                                                                ##STR65##                                                  169 NCH.sub.3                                                                          Cl H  CH.sub.3                                                                         CH.sub.2OC.sub.6 H.sub.5                                  __________________________________________________________________________

                  TABLE VI                                                        ______________________________________                                         ##STR66##                                                                      Compound        R.sub.24   Q                                                ______________________________________                                        170           H                                                                                         ##STR67##                                             171         CH.sub.3   CH.sub.2OC.sub.6 H.sub.5                             172           H          CH.sub.2OC.sub.6 H.sub.5                             ______________________________________                                    

                                      TABLE VII                                   __________________________________________________________________________     ##STR68##                                                                    Compound                                                                            Z.sub.2                                                                          R.sub.25                                                                         R.sub.26                                                                          Q                                                             __________________________________________________________________________    173   O  H  Cl  CH.sub.2CCI                                                   174   O  H  Cl  CH.sub.2CH.sub.2OH                                            175   O  Cl H   CH.sub.2CH.sub.2OCONHCH.sub.3                                 176   O  Cl Cl  CH.sub.2CCI                                                   177   O  H  H   CH.sub.2CCI                                                     178 S  H  Cl                                                                                 ##STR69##                                                      179 S  Cl Cl  CH.sub.2CH.sub.2OCONHC.sub.6 H.sub.4 Cl(4)                    180   S  H  Cl  CH.sub.2CH.sub.2OH                                            __________________________________________________________________________

                                      TABLE VIII                                  __________________________________________________________________________     ##STR70##                                                                    Compound R.sub.27     Q                                                       __________________________________________________________________________    181      OCOCH.sub.3  CH.sub.2OC.sub.6 H.sub.5                                182      OCOCH.sub.3  CH.sub.2OC.sub.6 H.sub.4 Cl(4)                          183      OCONHCH.sub.3                                                                              CH.sub.2OC.sub.6 H.sub.5                                184      OCOC.sub.2 H.sub.5                                                                         CH.sub.2OC.sub.6 H.sub.4 (NO.sub.2)                       185    OCOCH.sub.2Cl                                                                               ##STR71##                                              186      OCONHC.sub.2 H.sub.5                                                                       CH.sub.2CH.sub.2OC.sub.6 H.sub.3Cl.sub.2 (2,4)              187  OCONHC.sub.3 H.sub.7 (i)                                                                    ##STR72##                                                  188  OCONHC.sub.4 H.sub.9 (n)                                                                   CH.sub.2CH.sub.2N(C.sub.2 H.sub.5).sub.2                __________________________________________________________________________

                                      TABLE IX                                    __________________________________________________________________________     ##STR73##                                                                    Compound                                                                            Z.sub.3                                                                              R.sub.28                                                                         X    Q                                                        __________________________________________________________________________    189   S      H  CN   CH.sub.2OC.sub.6 H.sub.5                                   190 S      H  Cl                                                                                  ##STR74##                                                 191 S      H  CN   CH.sub.2CH.sub.2OH                                       192   S      H  CN   CH.sub.2CH.sub.2OCONHCH.sub.3                            193   S      Cl CN   CH.sub.2OC.sub.6 H.sub.3(CH.sub.3).sub.2(2,3)            194   S      Cl CH.sub.3                                                                           CH.sub.2OC.sub.6 H.sub.4Cl(4)                            195   O      Cl CN   CH.sub.2CH.sub.2OH                                       196   O      Cl CH.sub.3                                                                           CH.sub.2CH.sub.2OH                                         197 O      Cl Cl                                                                                  ##STR75##                                                 198 O      H  CN   CH.sub.2CH.sub.2OH                                       199   O      H  CN   CH.sub.2CH.sub.2OCONHCH.sub.3                            200   O      H  CH.sub.3                                                                           CH.sub.2CH.sub.2OH                                       201   O      H  CH.sub.3                                                                           CH.sub.2CH.sub.2OCONHC.sub.6 H.sub.5                       202 O      H  Cl                                                                                  ##STR76##                                                  203                                                                              O      H  CN   CHCCI                                                    204   NCH.sub.3                                                                            H  CN   CH.sub.2CH.sub.2OH                                       205   NCH.sub.3                                                                            H  CN   CH.sub.2CH.sub.2OCOC.sub.2 H.sub.5                       206   NCH.sub.3                                                                            H  CH.sub.3                                                                           CHCCI                                                      207 S      Cl CN                                                                                  ##STR77##                                                 208 S      Cl CN                                                                                  ##STR78##                                               __________________________________________________________________________

FORMULATION EXAMPLES EXAMPLE 4

Dusts:

The following substances are used to formulate (a) 5% and (b) a 2% dust:

(a) 5 parts of active substance, 95 parts of talc;

(b) 2 parts of active substance, 1 part of highly dispersed silicicacid, 97 parts of talc.

The active substances are mixed with the carriers and ground and in thisform can be processed to dusts for application.

EXAMPLE 5

Granulate:

The following substances are used to formulate a 5% granulate:

5 parts of active substance,

0.25 part of epichlorohydrin,

0.25 part of cetyl polyglycol ether,

3.25 parts of polyethylene glycol,

91 parts of kaolin (particle size of 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and the mixture isdissolved in 6 parts of acetone. Then polyethylene glycol and cetylpolyglycol ether are added. The resultant solution is sprayed on kaolinand the acetone is evaporated in vacuo.

EXAMPLE 6

Wettable powders:

The following constituents are used to formulate (a) a 70%, (b) a 40%,(c) and (d) a 25% and (e) a 10% wettable powder:

(a) 70 parts of active substance, 5 parts of sodiumdibutylnaphthylsulfonate, 3 parts of naphthalenesulfonicacid/phenolsulfonic, acid/formaldehyde condensate (3:2:1), 10 parts ofkaolin, 12 parts of Champagne chalk.

(b) 40 parts of active substance, 5 parts of sodium ligninsulfonate, 1part of sodium dibutylnaphthalenesulfonic acid, 54 parts of silicicacid.

(c) 25 parts of active substance, 4.5 parts of calcium ligninsulfate,1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5parts of sodium dibutylnaphthalenesulfonate, 19.5 parts of silicic acid,19.5 parts of Champagne chalk, 28.1 parts of kaolin.

(d) 25 parts of active substance, 2.5 parts ofisooctylphenoxy-polyethylene-ethanol, 1.7 parts of a Champagnechalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodiumaluminium silicate, 16.5 parts of kieselguhr, 46 parts of kaolin.

(e) 10 parts of active substance, 3 parts of a mixture of the sodiumsalts of saturated fatty alcohol sulfates, 5 parts ofnaphthalenesulfonic acid/formaldehyde condensate, 82 parts of kaolin.

The active substances are intimately mixed in suitable mixers with theadditives and ground in appropriate mills and rollers. Wettable powdersof excellent wettability and suspension power are obtained. Thesewettable powders can be diluted with water to give suspensions of thedesired concentration and can be used in particular for treating partsof plants.

EXAMPLE 7

Emulsifiable concentrate:

The following substances are used to formulate a 25% emulsifiableconcentrate:

25 parts of active substance

2.5 parts of epoxidised vegetable oil

10 parts of an alkylarylsulfonate/fatty alcohol polyglycol ether mixture

5 parts of dimethyl formamide

57.5 parts of xylene.

By diluting such a concentrate with water it is possible to prepareemulsions of the desired concentration, which are especially suitablefor leaf application.

BIOLOGICAL EXAMPLES EXAMPLE 8 Pre-emergence antidote test (basic test)

General test method:

Small flower pots (diameter 6 cm at the top) are filled with garden soilinto which the plant seed is sown, covered with the soil and gentlypressed firm. Then the antidote is sprayed as test substance in the formof a dilute solution (obtained from a wettable powder) in an amountcorresponding to 4 kg/ha. The herbicide is sprayed onto the soildirectly afterwards in corresponding amount. After the pots have stoodfor 18 days at about 20°-23° C. and 60°-70° C. relative humidity,evaluation is made in accordance with a linear scale from 1 (denotingtotal damage to the plant) to 9 (denoting undamaged healthy plant).Plants without antidote protection are used as control.

The following herbicides and plants were employed:

(1) 1.5 kg/ha of α-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionic acidn-butoxyethyl ester in maize of the "Orla 264" variety.

(2) 1.5 kg/ha ofMetolachlor=N-(-1-methyl-2-methoxyethyl)-N-chloroacetyl-2-ethyl-6-methylanilinein sorghum of the "Funk G-522" variety.

(3) 2 kg/ha ofPrometryn=2,4-bis(isopropylamino)-6-methyl-thio-s-triazine in soybeans.

(4) 2 kg/ha of 4-ethylamino-6-tert-butylamino-2-chloro-s-triazine inwheat of the "Farnese" variety.

(5) 4 kg/ha ofPrometryn=2,4-bis(isopropylamino)-6-methyl-thio-s-triazine in sorghum ofthe "Funk G-522" variety.

(6) 2 kg/ha of α-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionic acidn-butoxyethyl ester in barley of the "Mazurka" variety.

In these tests, the antidote action was e.g. as follows:

    ______________________________________                                                             Rating of the herbicidal action                          Test variant                                                                             Compound  (without/with antidote)                                  ______________________________________                                        2          2         4/6                                                      2          76        3/9                                                      2          77        3/9                                                      3          5         2/6                                                      4          23        4/7                                                      5          15        3/7                                                      ______________________________________                                    

EXAMPLE 9 Antidote action on separate application(antidote/pre-emergence, herbicide/post-emergence)

General test method:

Small flower pots (diameter 6 cm at the top) are filled with sandy loaminto which the plant is sown. After covering the seed, a dilute solutionof the antidote as test substance is sprayed onto the surface of thesoil in an amount corresponding to 4 kg/ha. The pots are kept at 20°-23°C. and 60°-70° C. relative humidity. When the plants have attained the2- to 3-leaf stage after 10 days, they are treated as indicated belowwith the corresponding amount of herbicide. Evaluation is made 14 daysafter the application of the herbicide, using the same rating system asin Example 8. Plants unprotected by antidote are used as control.

The herbicides and plants employed are:

(1) 4 kg/ha ofAmetryn=2-ethylamino-4-isopropylamino-6-methylthio-s-triazine in maizeof the "Orla 264" variety.

(2) 1 kg/ha of Prometryn=2,4-bis(isopropylamino)-6-methylthio-s-triazinein sorghum of the "Funk G-522" variety.

(3) 0.25 kg/ha of α-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionicacid n-butoxyethyl ester in barley of the "Mazurka" variety.

A good antidote action was obtained in these tests with compounds of theformula (I). A rating of 2/6 was obtained in test variant 2 withcompound 84.

EXAMPLE 10 Antidote action in transplanted rice on separate application(antidote/pre-emergence, herbicide/post-emergence)

Plastic tubs measuring 8×8×10 cm are filled with wet marshy soil to 2 cmbelow the edge. A dilute solution of the antidote as test substance issprayed onto the surface of the soil in an amount corresponding to 4kg/ha. Rice plants of the "IR-88" variety are transplanted in the 11/2-to 2-leaf stage into the prepared tubs. On the next day, the water levelis raised to about 1.5 cm. Four days after transplantation,2-ethylamino-4-(1,2-dimethyl-n-propylamino)-6-methylthio-s-triazine isadded to the water in granule form in an amount corresponding to 0.75kg/ha. During the test, the temperature is 26°-28° C. and the relativehumidity 60°-80° C. Evaluation is made 20 days after the treatment withherbicide, using the same rating as in Example 8. Plants not protectedwith antidote are used as control. In this test, compounds 2, 9 and 79reduced the rating 4 of the herbicidal action to 8, 8 and 7 respectivelyof the antidote.

EXAMPLE 11 Pre-emergence antidote test in nutrient solution

A Hewitt nutrient solution, which contains the amount of herbicideindicated below as well as 10 ppm of the antidote to be tested, isprepared.

Seeds which would normally be damaged in the indicated testconcentrations of the herbicide employed are sown in granular zonolith(expanded vermiculate) in plastic flower pots (diameter 6 cm at the top)which are perforated at the bottom. Each pot is then placed in a secondtransparent plastic flower pot (diameter 7 cm at the top) which containsabout 50 ml of the nutrient solution prepared with herbicide andantidote. This nutrient solution then rises by capillary action in thefilling material of the smaller pot and moistens the seed and thegerminating plant. The loss in fluid is daily replenished to 50 ml withpure Hewitt nutrient solution. Evaluation is made 3 weeks after thestart of the test, using the same rating as in Example 8. The controlsolution employed in the parallel test contains no additive.

The herbicides and plants employed are:

(1) 4 ppm of Prometryn=2,4-bis(isopropylamino)-6-methylthio-s-triazinein sorghum of the "Funk G-522" variety.

(2) 4 ppm of 4-ethylamino-6-tert-butylamino-2-chloro-s-triazine in wheatof the "Farnese" variety.

(3) 4 ppm of α-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionic acidn-butoxyethyl ester in barley of the "Mazurka" variety.

(4) 5 ppm ofMetolachlor=N-(1-methyl-2-methoxyethyl)-N-chloroacetyl-2-ethyl-6-methanilinein sorghum of the "Funk G-522" variety.

The antidote action obtained in these tests is e.g. as follows:

    ______________________________________                                                             Rating of the herbicidal action                          Test variant                                                                             Compound  without/with antidote                                    ______________________________________                                        2          23        4/7                                                      2          78        3/6                                                      4          23        4/7                                                      5          82        1/6                                                      ______________________________________                                    

EXAMPLE 12 Pre-emergence antidote test in nutrient solution (rice)

A Hewitt nutrient solution, which additionally contains 10 ppm of theantidote to be tested, is prepared.

Rice seeds of the "IR-8" variety are sown in granular filling material(granular zonolith) in plastic flower pots (diameter 6 cm at the top)which are perforated at the bottom. Each pot is then placed in a secondtransparent plastic flower pot (diameter 7 cm at the top) which containsabout 50 ml of the nutrient solution prepared from herbicide andantidote. This nutrient solution then rises by capillary action in thefilling material of the smaller pot and moistens seed and plant. Theloss in fluid is daily replenished to 50 ml with pure Hewitt solution.After 15 days, the rice plants are transplanted in the 2- to 21/2-leafstage in rectangular plastic pots (8×8×10 cm) which are filled with 500ml of wet, marshy soil. The water level is increased next day to 1-2 cmabove the level of the soil. Four days after transplantation, theherbicide2-ethylamino-4-(1,2-dimethyl-n-propylamino)-6-methylthio-s-triazine isadded in granule form in an amount corresponding to 0.75 kg/ha.Evaluation is made 3 weeks later in accordance with the rating employedin Example 8 and subsequent Examples. The control solution used in theparallel test contains no antidote. A good antidote action was obtainedin this test with the compounds of the formula (I), in particular withcompounds 2, 9, 79 and 81.

EXAMPLE 13 Post-emergence antidote test in nutrient solution

General test method:

Small plastic flower pots (diameter 6 cm at the top), which areperforated at the bottom, are filled with granular zonolith and theseeds are sown in this material. Each pot is then placed in a secondtransparent plastic flower pot (diameter 7 cm at the top) which contains50 ml of water which rises by capillary action and moistens the seed.Form the 5th day, the continual loss in water is made up with Hewittnutrient solution. From the 15th day, when the plant is in the11/2-2-leaf stage, 10 ppm of the antidote to be tested and the amount ofherbicide indicated below are added to the nutrient solution which hasbeen again replenished to 50 ml. From the 16th day, the loss in fluid isagain made up with pure Hewitt nutrient solution. During the entireduration of the test, the temperature is 20°-23° C. and the relativehumidity 60°-70° C. Evaluation is made 3 weeks after the addition of theherbicide in accordance with the rating employed in Example 8 andsubsequent Examples.

Test variants:

(1) 15 ppm of α-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionic acidpropargylthiolo-ester in wheat of the "Zenith" variety.

(2) 4 ppm of 4-ethylamino-6-tert-butylamino-2-chloro-s-triazine in wheatof the "Zenith" variety.

(3) 2 ppm of α-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionic acidn-butoxyethyl ester in maize of the "Orla" variety.

(4) 8 ppm of α-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionic acidn-butoxyethyl ester is sorghum of the "Funk G-522" variety.

(5) 4 ppm of Prometryn=2,4-bis(isopropylamino)-6-methylthio-s-triazinein sorghum of the "Funk G-522" variety.

(6) 8 ppm of α-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionic acidmethyl ester in wheat of the "Zenith" variety.

A good antidote action is obtained in these tests with compounds of theformula (I). The results are as follows:

    ______________________________________                                                             Rating of the herbicidal influence                       Test variant                                                                             Compound  without/with antidote                                    ______________________________________                                        1           5        4/7                                                      2          23        4/7                                                      2          78        3/6                                                      ______________________________________                                    

EXAMPLE 14 Antidote test--seed soaking

Rice seeds of the "IR-8" variety are immersed for 48 hours in solutionsof the test substances in concentrations of 10, 100 or 1000 ppm. Theseeds are then allowed to dry for about 2 hours until they are no longertacky. Rectangular plastic tubs (8×8×10 cm) are filled with sandy loamto 2 cm below the edge. 4 g of seeds are sown in each tub and only veryloosely covered (to about the diameter of the seed). The soil is kept ina moist (non-marshy) state. Then a dilute solution of the herbicideN-(1-methyl-2-methoxymethyl)-N-chloroacetyl-2-ethyl-6-methylaniline isapplied in an amount corresponding to 1.5 kg/ha. Evaluation is made 7and 18 days after transplantation in accordance with the rating employedin Example 8 and subsequent Examples. A good antidote action is obtainedin this test with compounds of the formula (I), in particular withcompounds 9 (3/6), 80 (3/6), 155 (2/6), 157 (2/6) and 41 (2/6).

EXAMPLE 15 Antidote test (root dipping)

Rice plants of the "IR-8" variety are reared in soil until they are inthe 11/2- to 2-leaf stage and then superficially washed. Then only theroots of the plants, in bunches, are dipped for 45 minutes in a dishcontaining solutions of the test substance in a concentration of 10, 100or 1000 ppm. The plants are then transplanted in sandy loam incontainers measuring 47×29×24 cm. The surface of the soil is coveredwith water to a height of 11/2 to 2 cm. One day after transplantation, adilute solution of the herbicideN-n-propoxyethyl-N-chloroacetyl-2,6-diethylaniline is pipetted directlyinto the water in an amount corresponding to 1.5 kg/ha. Evaluation ismade 7 and 18 days after transplanation in accordance with the ratingemployed in Example 8 and subsequent Examples. Good antidote action isobtained in this test with compounds of the formula (I).

What is claimed is:
 1. A method of protecting sorghum and rice cropsfrom the phytotoxic action of 1,3,5-triazine or haloacetanilideherbicides, which comprises adding to the herbicide or applying to thelocus of the crops, as antidote, a compound of the formula ##STR79##wherein Ar is 1-naphthyl or ##STR80## in which R₁ is hydrogen, loweralkyl, lower alkoxy or halogen, and R₂ is hydrogen or lower alkyl, andR₈ is phthalimido or tetrahydrophthalimido, in a plant-protectingamount.
 2. A method according to claim 1 in which, in the compound,Ar is1-naphthyl, phenyl or 4-chlorophenyl, and R₈ is phthalimido.
 3. A methodaccording to claim 1 in which the herbicide isN-(1-methyl-2-methoxyethyl)-N-chloroacetyl-2-ethyl-6-methylaniline,2,4-bis(isopropylamino)-6-methylthio-s-triazine, or2-ethylamino-4-(1,2-dimethyl-n-propylamino)-6-methylthio-s-triazine. 4.A method according to claim 2 in which the compound isphenylacetonitrile-oxime-phthalimidomethyl ether.
 5. A method accordingto claim 4 in which the herbicide is2-ethylamino-4-(1,2-dimethyl-n-propylamino)-6-methylthio-s-triazine andthe plant is rice.
 6. A method according to claim 4 in which theherbicide isN-(1-methyl-2-methoxyethyl)-N-chloroacetyl-2-ethyl-6-methyl-aniline andthe plant is rice.
 7. A method according to claim 2 in which thecompound is 4-chlorophenylacetonitrile-oxime-phthalamidomethyl ether. 8.A method according to claim 7 in which the herbicide is2,4-bis(isopropylamino)-6-methylthio-s-triazine and the plant issorghum.